Polyhydric alcohol esters



Patented Dee. 1, i936 v 2 2 918 w UNITED STATES PATENTOFFICE POLYHYDBIC ALCOHOL ESTERS Walter E. Lawson, Woodbury, N. J., assignor to E.. -I. do Pont de Nemours & Company, Wilmington, Deb, a corporation of Delaware No Drawing. Application March 28, 19st Serial No. 13,485

16 Claims. (01. zooce) This invention relates to new compositions of tion for 6 hrs. The product was finally washed matter, more particularly to monocarboxylic acid with boiling water and-then recrystallized three esters of long chain polyhydric alcohols having times from ethyl acetate. The white crystalline at least three hydroxyl groups. The invention octadecanetriol melted at 80-81 C.

r further relates to plasticized compositions con- A mixture of twenty-four parts by weightof 5 taining cellulose derivatives and these esters. In octadecanetriol and 240 parts by weight of acetic its preferred form this invention relates to esters anhydride were refluxed for 26 hrs. An oily layer of polyhydric'alcohols obtainable by the perac'etwas thrown out by dilution with water and then ylation or other peracylation of higher unsatuthoroughly washed with water until neutral. The

10 rated alcohols suchas oleyl alcohol. oily layer was diluted with etheigtreated with 10 The esters of the present invention may be charcoal and dried over sodium sulfate. vAfter made by the following general methods: removing the ether on the steam bath the light (1) Peracylation of an unsaturated alcohol to brown oil was heated in a.-..vacuum oven for 3 obtain a monoester followed by further esterifihrs.- The oil had an acid number of 1.2 and-a cation with a monobasic acid, for example, treatsaponification number of 3'75, which indicates a 15 ment of oleyl alcohol withperacetic acid to obtain purity of 95.5% of the triacetate of octadecanethe monoacetate of octadecanetriol which is then triol. This ester wasinsoluble in water, but soluacetylatedto obtainthe triacetate of cctadecaneble in acetic acid, ether, acetone, ethyl acetate, triol. toluene, and gasoline.

(2) Hydroxylation of polyunsaturated alcohols Exam le 2 20 such as linoleyl alcohol followed by esterlflcation, p v as for example, the hydroxylation of linoleyl al- One part by weight of ethyl cellulose dissolved cohol will yield a trihydroxy alcohol which on in 11 parts by weight of a toluene-ethyl alcohol esterification will yield a tri-ester. The hydroxmixture, '1 parts of toluene -and 1 part of octaylation may be carried outfor example by sulfadecanetriol triacetate were blended together to 25 tion of the unsaturated alcohol followed by hygive a clear lacquer base. Further dilution with drolysis in dilute acid solution. toluene gave a lacquer of spraying viscosity which (3) Addition of hypochlorous acid to an; unyielded clear, flexible films. saturated alcohol followed by treatment with an Example" 3 acid anhydride and sodium acetate to convert to the polyacetate. for example, condensation of One part of nitrocellulose in 3 parts of a solvent oleyl alcohol with hypochlorous acid and convermixture containing essentially butyl acetate, 3 sion of the resulting chlorohydrin to the triaceparts of butyl acetate and 1 part of octadecanetatetriol triacetate were blended together to give a Having outlined above the general methods of clear lacquer which yielded clear, flexible films. 35 preparation, the following exemplifications therea of are added for purposes ofillustration but not Example 4 inlimitation: One part of cellulose acetate dissolved in 5.7

' Mm parts of a solvent mixture containing essentially. 40 Example g:::;:; made tnol acetone was diluted with 6.7 parts of acetone and 4 1 part of octadecanetriol triacetate added. This Two hundred sixteen parts by weight of pure yielded a compatible lacquer. On evaporation of oleyl alcohol, 1200 cc. of glacial acetic acid and the solvent, the residue was a tough plastic n a- 456 g. of 30% hydrogen peroxide were placed in terial suitable for formation into rods, tubes, and

a two-liter, three-neck flask and heghted with 9. sheets. 45

water bath to 'l5-80 C. for 2 hrs. e product was washed with water to remove acetic acid and q f dgf zzggfig monoacetate and the hydrogen peroxide. Ethyl acetate was added I' s l to dissolve the wan material and the solution' Two hundred sixty-eight parts by weight of washed with boiling water until neutral. The oleyl alcohol, 228 partsby weight of 30% hydrogen 5o solvent was thenremoved by evaporation and the peroxide and 600 parts by weight of glacial acetic remaining oil had an iodine number of 4. The acid were heated in a 2 liter flask with stirring at oil was next treated with hot water containing 80 C. for 13 hrs. The product was washed three alkali until neutral and then boiled with 50 g. of times with salt water, diluted with ether, and the 6 sodium hydroxide in 500 cc. of water with agitaether solution dried with sodium sulfate. After 5 decanetriol is 163. The monoacetate of octadecanctriol is soluble in benzene, ethyl acetate, ether, and acetone, but is insoluble in water. It is compatible with nitrocellulose. Two hundred seventy-six parts by weight of the monoacetate of octadecanetriol, 900 parts by weightof acetic anhydride and a small amount of hydrogen chloride were heated under a reflux condenser 6 hrs. at l-1l0 C. and finally 4 hrs. at 125-l30 C. The product was washed with water, dissolved in ether, the ether solution dried with sodium sulfate, filtered, and the ether evaporated. Two hundred seventy parts by weight of light-brown oil with a saponification number of 356 and an acid number of "I was obtained. This oil was fractionated and the main fraction distilled over at 190-204 C. at 1 mm. as a straw-colored oil.

Example 6.Peracetulotion 0f ricifiole'yl alcohol One hundred forty-two parts by weight of ricinoleyl alcohol obtained by sodium reduction of ethyl ricinoleate, 114 parts by weight of 30% hydrogen peroxide, and 300 parts by weight of glacial acetic acid were stirred under reflux at 80-90 C. for hrs. The product was diluted with ether, washed with water to remove the unreacted acetic acid and the ether solution dried with sodium sulfate. After filtering, the ether was evaporated and the straw-colored oil which remained had. an iodine number of 11, whereas the original alcohol had an iodine number of 92.5. The product was the monoacetate ester of octadecanetetrol-l,9,10,12 and was used in plasticizing nitrocellulose compositions. This product was treated with a mixture of acetic acid and acetic anhydride and converted to the tetraacetate of octadecanetetrol, a viscous oil insoluble in water'but soluble in esters, ketones, and hydrocarbons, and being a plasticizer for nitrocellulose.

Example 7.'-Mi:rtare of triacetate: of C12, c, 010,

' C11. C20, C22 friols A mixture containing 345 g. of technical octadecanetriol monoacetate, 200 g. acetic acid, 300 g.

ethylene dichloride, 2 g. sulfuric acid were heated to boiling in an apparatus designed to separate water from the distillate and to return the ethyrlene dichloride to the reaction vessel. Distillation was continued until the theoretical amount of water had been removed. The product was washed with sodium carbonate solution to remove excess acid and was refined by heating to 130 C. under 50 mm. pressure to remove volatile material. The resulting product was treated with decolorizing carbon and filtered. A light-colored oil resulted. This was insoluble in water but soluble in esters, ketones and hydrocarbons. It was particularly well suited as a plasticizer for nitrocellulose. The technical octadecanetriol monoacetate used in this example was made from the technical alcohol obtained by the carboxylic hydrogenation of sperm oil andhad the following approximate composition; unsaturated-alcohols C]: 0.8%; 014 0.4%; Cu 21.4%; oleyl 34.9%; 020 12.4%; C2:

0 0.4%; and saturated alcohols C16 1%; G1: 3.7%;

C14 5.9%; Cu 4.9%; 01'. 72%; c 0.7%.

Example 8.-Octodecanetriol trildurate melting solid which is soluble in benzene and ether.

Example 9 1 Ninety-three parts by weight of an unsatura alcohol, obtained by sodium reduction of China wood 01], which had an iodine number of 176, was

dissolved in 600 parts by weight of glacial acetic acid and 200 parts by weight of hydrogen peroxide. The mixture was heated under a reflux condenser at 75 C. for 6 hrs. and then left to stand at room temperature three days. The acetic acid solution was diluted with salt water and the oil washed several times with water to remove unreacted hydrogen peroxide and acetic acid. The oil was diluted with toluene and the water was removed by distilling off the water-toluene binary. Removal of the toluene by distillation leaves an oily product which is an octadecanepentol diacetate which is soluble in esters and hydrocarbons, insoluble in water, and is a plasticizer for cellulose derivatives. One hundredseventeen parts by weight of this dlacetate ester, 240 parts by weight of glacial acetic acid, 3 parts by weight of sulfuric acid, and 500 cc. of toluene were heated under a 4 ft. column until all of the water of reaction was removed. The reaction mixture was washed with water and the toluene evaporated. The resulting oil had a saponification number of 340, indicating three of the five possible hydroxyl groups were esterified. This octadecanepentol triacetate is soluble in ethyl acetate, toluene, ether, and acetone, and is insoluble in water. It

plasticizes nitrocellulose compositions.

, Altho certain acids have been disclosed in the examples, monocarboxylic acids in general may-- be employed. These include aliphatic, alicyclic, heterocyclic and aromatic, saturated and unsaturated, substituted and unsubstituted, branched or straight chain acids such as acetic, propionie, isobutyric, butyric, lauric, oleic, stearic, palmitic, arachidic, branched chain acids corresponding to the higher alcohols, obtained as a by-product 'of the methanol synthesis, capric, caprylic,

erally applicablein the preparation of from alcohols of 11 to 22 carbon atoms having at least three hydroxyl groups. These alcohols may be prepared by the per'acylation of unsaturated alcohols such as phytol.

The invention is most feasibly applicable to the esterification of has turated alcohols deriv- 1s able by carboxyl reductionof fats and oils, containing 11 to 22 carbon atoms and preferably those containing approximately 18' carbon.

atoms. The alcohols below 11 do not give :1 M ficiently non-volatile ester for satisfactory plasticization. Those within the range Etc 22 have a combination of low volatility and adequately high solvent power for cellulose derivatives.

acetate is not. The invention is thus applicable to undecylenyl alcohol, to oleyl alcohol, or the mixture of unsaturated alcohols obtainable by sodium reduction of sperm whale oil, eleostearyl alcohol obtained by sodium reduction of elecstearic acid esters, linoleyl alcohol obtained by sodium reduction of methyl linoleate, and ricinoleyl alcohol obtained by sodium reduction of ethyl ricinoleate. Undecylenyl alcohol yields an undecanetriol, oleyl alcohol yields and octadecanetriol, ricinoleyl alcohol yields an octadecanetetrol, linoleyl alcohol yields an octadecanepentol, and eleostearyl alcohol yields an octadecaneheptol. The invention is also applicable to the preparation of esters fiom polyolefines by peracylation followed by a completion of the acylation. Diolcfines which are especially useful as intermediates for peracylation'are, for."

example, the diolefines which result from the CH:(CH2) 1CH=CH(CH2) scn=crn from oleyl alcohol. A particularly suitable source of unsat urated alcohols for dehydration is the mixtmre of alcohols obtained by the carboxyl reduction of sperm whale oil. Any of these polyhydric alcohols or mixtures thereof and polyhydric alco-. .hols generally having from 11 to 22 carbon atoms and having at least three hydroxyl groups may be used with any of the above acids or mixturm thereof in the preparation of esters suitable for use in the-manufactm'e of plasticized compositions. All of theesters prepared in this nmn ner are substanifially non-volatile and have been found to be satisfactory-plasticizers for cellulose derivatives, and natural and synthetic resins.

Thus they may be used with orwithout solvenm r t al 1'! s such as suitable mixtures es ers cohols an B it-least med by a monohydrocarbons in coating or plastic compositions containing cellulose esters such as cellulose nitrate, cellulose propionate, cellulose butyrate,

cellulose isobutyrate, cellulose crotonate, cellulose acetobutyrate, and cellulose others such as ethyl cellulose, benzyl cellulose, glycol cellulose, etc, with natural resins such as synthetic resins such as phenol aldehyde resins, polystyrene resins, resins produced by condensation of ketones, ether resins etc., and drying and simidrying oils, e. g. castor oil. WaxB such as paraflin wax, pigments, plasticizers such as dibutylphthalate, and organic fillers such as wood flour-or cellulose may alsobe employed in these coating or plastic compositions.

The new compounds when employed as plasticizers may be .used in any amount from 5 to 200% based upon lulose derivatives'or natural and syntheticreains', Q

. thesco dehydration of unsaturated alcohols, e. g., De

remaining oils, pigments, and filling materials. Specifically they may be used in the preparation of lacquers and enamels for coating metals, wood, and. pa-

per, in dopes for coating fabrics, in moistureproof lacquers for coating regenerated in plastic compositions to be used in the preparation of toiletware, novelties, sheeting, rods, tubes, safety glass interlayers, etc.,- and, in lacquers for coating wire screens and in the preparation of thin sheets for wrapping purposes.

An advantage of this invention is that it furnishes extremely high-boiling, water-resistant plasticizers. Some of these materials give extremely tough plastic compositions when used with cellulose derivafives'and the products produced are substantially permanently flexible.

Whereas polybasic acid esters of polyhydric alcohols are readily converted to infusible, insoluble products unsuited for use as plasticizers, it has been found that the monobasic acid esters of long chain polyhydric alcohols do not become mfusible and insoluble in organic solvents'but are eminently suitable as plasticizers.

The esters of the present invention may be generally described as esters of a polyhydric alcohol of the formula;

anagra mthisformulanisfromlltofiandzisat least three but is-preferably less than 15. The abovedescription and examples are intended to be illustrative only. Any modification of or variation therefrom which conforms to the spirit of thejn'venfion is intended. to be included of the claims. Iclaim:

1. An ester wherein ofthehydroayl groups.

of a long chain aliphatic polyhydric alcohol of the'formulav Cerium-(6K): j

whereinzis'atleast3andnisl1to22,are-

'esterifiedvby a monocarboxylic acid.

2-. An estercmnpositionwherein a of same alcohols containing 12, 14, 16, is, 20 and ,22 carbon atoms have all of the hydroxyl groups of the alcohols esterified'by a monocarboxylic acid.

3. Anester whereinall of the groups of along chain aliphatic ldric alcoholof the formula Callas-(010:

carboxylic acid.

4. Satmated esters prepared by the peracyla-. tion of imsaturated alcohols of 11 to 22 carbon atoms followed by complete esteriflcation of the remaining hydroxyl groups by'means of a monobosic carboxylic' acid.

5. Saturated esters P epared by the peracetylation of unsaturated alcohols of 11 to 22 carbon atoms followed by complete esteriflcation of the hydroxy groups by means of a mono-. basic carboxylic acid.

6. Anesterwhereinallofthehydroxyl'grmips of a long chain aliphatic n lyhydric alcohol of the formula v C inic-(0E3 wherein;isatlcasl;3,areestei-ifledbyanaliphatic monocarbnmlic acid.

"I. Anesterwhereinallofthehydroxylaroups ofalongcbainaliphaticp b y rlcalcoholoithe formula CiaHsa-c (OH) 2 wherein a: is at 1east-3 are estcrifled by a saturated aliphatic monocarboxylic acid.

8. An ester wherein all of the hydroxyl groups of a long chain aliphatic polyhydric alcohol of the formula (Julia-ACE):

wherein a: is at' least 3, are esterified by acetic acid.

9. An este'r wherein a plurality of the hydroxyl groups of a long chain aliphatic p'olyhydric alcohol of the formula wherein a: is at least 3, is esterifled by lauric acid. 10, An ester of octadecanetriol-1,9,10 wherein all of the hydroxyl groups are esterified by a monocarboxylic acid.

aoeaois hydroxyl groups by means of a monobasic carboxylic acid.

16. Process for the preparation'of saturated esters which comprises peracylating an unsaturated alcohol of 11 to 22 carbon atoms and thereafter completely esterifying the remaining hydroxyl groups by means of a monobasic carboxylic acid.

WALTER E. LAWSON. 

